EP1851173A1 - Removal of organic pollutants from contaminated water - Google Patents
Removal of organic pollutants from contaminated waterInfo
- Publication number
- EP1851173A1 EP1851173A1 EP06728167A EP06728167A EP1851173A1 EP 1851173 A1 EP1851173 A1 EP 1851173A1 EP 06728167 A EP06728167 A EP 06728167A EP 06728167 A EP06728167 A EP 06728167A EP 1851173 A1 EP1851173 A1 EP 1851173A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- clay
- complex
- organic cation
- granular material
- micelles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002957 persistent organic pollutant Substances 0.000 title claims description 12
- 239000004927 clay Substances 0.000 claims abstract description 129
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 239000000693 micelle Substances 0.000 claims abstract description 58
- 150000002892 organic cations Chemical class 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000008187 granular material Substances 0.000 claims abstract description 32
- 230000007935 neutral effect Effects 0.000 claims abstract description 27
- 125000000129 anionic group Chemical group 0.000 claims abstract description 22
- 239000003344 environmental pollutant Substances 0.000 claims description 54
- 231100000719 pollutant Toxicity 0.000 claims description 53
- 239000004009 herbicide Substances 0.000 claims description 26
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 claims description 22
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 claims description 22
- 239000005981 Imazaquin Substances 0.000 claims description 20
- -1 pheny Chemical group 0.000 claims description 19
- 239000004576 sand Substances 0.000 claims description 18
- 239000005494 Chlorotoluron Substances 0.000 claims description 13
- JXCGFZXSOMJFOA-UHFFFAOYSA-N chlorotoluron Chemical compound CN(C)C(=O)NC1=CC=C(C)C(Cl)=C1 JXCGFZXSOMJFOA-UHFFFAOYSA-N 0.000 claims description 13
- OORLZFUTLGXMEF-UHFFFAOYSA-N sulfentrazone Chemical compound O=C1N(C(F)F)C(C)=NN1C1=CC(NS(C)(=O)=O)=C(Cl)C=C1Cl OORLZFUTLGXMEF-UHFFFAOYSA-N 0.000 claims description 12
- CTSLUCNDVMMDHG-UHFFFAOYSA-N 5-bromo-3-(butan-2-yl)-6-methylpyrimidine-2,4(1H,3H)-dione Chemical compound CCC(C)N1C(=O)NC(C)=C(Br)C1=O CTSLUCNDVMMDHG-UHFFFAOYSA-N 0.000 claims description 11
- 239000004098 Tetracycline Substances 0.000 claims description 10
- 235000019364 tetracycline Nutrition 0.000 claims description 10
- 150000003522 tetracyclines Chemical class 0.000 claims description 10
- 239000003242 anti bacterial agent Substances 0.000 claims description 9
- 229940088710 antibiotic agent Drugs 0.000 claims description 9
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 6
- 239000002509 fulvic acid Substances 0.000 claims description 6
- 238000011534 incubation Methods 0.000 claims description 6
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 5
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229940095100 fulvic acid Drugs 0.000 claims description 5
- 239000004021 humic acid Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 229910021647 smectite Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 229940040944 tetracyclines Drugs 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- NUPJIGQFXCQJBK-UHFFFAOYSA-N 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-5-(methoxymethyl)nicotinic acid Chemical compound OC(=O)C1=CC(COC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 NUPJIGQFXCQJBK-UHFFFAOYSA-N 0.000 claims description 2
- CLQMBPJKHLGMQK-UHFFFAOYSA-N 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)nicotinic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC=CC=C1C(O)=O CLQMBPJKHLGMQK-UHFFFAOYSA-N 0.000 claims description 2
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical class O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims description 2
- PVSGXWMWNRGTKE-UHFFFAOYSA-N 5-methyl-2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]pyridine-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC=C(C)C=C1C(O)=O PVSGXWMWNRGTKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005472 Bensulfuron methyl Substances 0.000 claims description 2
- 239000005496 Chlorsulfuron Substances 0.000 claims description 2
- 239000005508 Dimethachlor Substances 0.000 claims description 2
- 239000005566 Imazamox Substances 0.000 claims description 2
- XVOKUMIPKHGGTN-UHFFFAOYSA-N Imazethapyr Chemical compound OC(=O)C1=CC(CC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 XVOKUMIPKHGGTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005567 Imazosulfuron Substances 0.000 claims description 2
- NAGRVUXEKKZNHT-UHFFFAOYSA-N Imazosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N3C=CC=CC3=NC=2Cl)=N1 NAGRVUXEKKZNHT-UHFFFAOYSA-N 0.000 claims description 2
- JLLJHQLUZAKJFH-UHFFFAOYSA-N Isouron Chemical compound CN(C)C(=O)NC=1C=C(C(C)(C)C)ON=1 JLLJHQLUZAKJFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005586 Nicosulfuron Substances 0.000 claims description 2
- GPGLBXMQFQQXDV-UHFFFAOYSA-N Primisulfuron Chemical compound OC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC(F)F)=CC(OC(F)F)=N1 GPGLBXMQFQQXDV-UHFFFAOYSA-N 0.000 claims description 2
- 229940100389 Sulfonylurea Drugs 0.000 claims description 2
- NBQCNZYJJMBDKY-UHFFFAOYSA-N Terbacil Chemical compound CC=1NC(=O)N(C(C)(C)C)C(=O)C=1Cl NBQCNZYJJMBDKY-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- ORFPWVRKFLOQHK-UHFFFAOYSA-N amicarbazone Chemical compound CC(C)C1=NN(C(=O)NC(C)(C)C)C(=O)N1N ORFPWVRKFLOQHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XOEMATDHVZOBSG-UHFFFAOYSA-N azafenidin Chemical compound C1=C(OCC#C)C(Cl)=CC(Cl)=C1N1C(=O)N2CCCCC2=N1 XOEMATDHVZOBSG-UHFFFAOYSA-N 0.000 claims description 2
- XMQFTWRPUQYINF-UHFFFAOYSA-N bensulfuron-methyl Chemical group COC(=O)C1=CC=CC=C1CS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 XMQFTWRPUQYINF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000005467 butylenyl group Chemical group 0.000 claims description 2
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical class NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 claims description 2
- VJYIFXVZLXQVHO-UHFFFAOYSA-N chlorsulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)Cl)=N1 VJYIFXVZLXQVHO-UHFFFAOYSA-N 0.000 claims description 2
- SCCDDNKJYDZXMM-UHFFFAOYSA-N dimethachlor Chemical compound COCCN(C(=O)CCl)C1=C(C)C=CC=C1C SCCDDNKJYDZXMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 125000006038 hexenyl group Chemical group 0.000 claims description 2
- 125000005980 hexynyl group Chemical group 0.000 claims description 2
- PUIYMUZLKQOUOZ-UHFFFAOYSA-N isoproturon Chemical compound CC(C)C1=CC=C(NC(=O)N(C)C)C=C1 PUIYMUZLKQOUOZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- MFOUDYKPLGXPGO-UHFFFAOYSA-N propachlor Chemical compound ClCC(=O)N(C(C)C)C1=CC=CC=C1 MFOUDYKPLGXPGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
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- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
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- OGQYJDHTHFAPRN-UHFFFAOYSA-N 2-fluoro-6-(trifluoromethyl)benzonitrile Chemical compound FC1=CC=CC(C(F)(F)F)=C1C#N OGQYJDHTHFAPRN-UHFFFAOYSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- MTERSQYMYBGZTP-UHFFFAOYSA-N 4-amino-n-(5-methyl-2-phenylpyrazol-3-yl)benzenesulfonamide Chemical compound C=1C=CC=CC=1N1N=C(C)C=C1NS(=O)(=O)C1=CC=C(N)C=C1 MTERSQYMYBGZTP-UHFFFAOYSA-N 0.000 description 1
- 241000208199 Buxus sempervirens Species 0.000 description 1
- NLYNUTMZTCLNOO-UHFFFAOYSA-N Chlorbromuron Chemical compound CON(C)C(=O)NC1=CC=C(Br)C(Cl)=C1 NLYNUTMZTCLNOO-UHFFFAOYSA-N 0.000 description 1
- 239000004099 Chlortetracycline Substances 0.000 description 1
- DHWRNDJOGMTCPB-UHFFFAOYSA-N Dimefuron Chemical compound ClC1=CC(NC(=O)N(C)C)=CC=C1N1C(=O)OC(C(C)(C)C)=N1 DHWRNDJOGMTCPB-UHFFFAOYSA-N 0.000 description 1
- 239000005510 Diuron Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005533 Fluometuron Substances 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000007230 Sorghum bicolor Nutrition 0.000 description 1
- ZLYHTQKHXIVMLY-UHFFFAOYSA-N Sulfatolamide Chemical compound NCC1=CC=C(S(N)(=O)=O)C=C1.NC(=S)NS(=O)(=O)C1=CC=C(N)C=C1 ZLYHTQKHXIVMLY-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000012984 antibiotic solution Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 1
- 229960000228 cetalkonium chloride Drugs 0.000 description 1
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 1
- 229960004475 chlortetracycline Drugs 0.000 description 1
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 1
- 235000019365 chlortetracycline Nutrition 0.000 description 1
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- 239000005446 dissolved organic matter Substances 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- RZILCCPWPBTYDO-UHFFFAOYSA-N fluometuron Chemical compound CN(C)C(=O)NC1=CC=CC(C(F)(F)F)=C1 RZILCCPWPBTYDO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000004746 geotextile Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010423 industrial mineral Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
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- 210000004080 milk Anatomy 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960004368 oxytetracycline hydrochloride Drugs 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- UEMLYRZWLVXWRU-UHFFFAOYSA-N sulfathiourea Chemical compound NC(=S)NS(=O)(=O)C1=CC=C(N)C=C1 UEMLYRZWLVXWRU-UHFFFAOYSA-N 0.000 description 1
- 229960004052 sulfathiourea Drugs 0.000 description 1
- 229960003356 sulfatolamide Drugs 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 1
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Definitions
- This invention relates to systems for removal of organic pollutants from water.
- Solubilization of organic pollutants by micelles of surfactants (6, 7) was the basis of the micellar-enhanced ultrafiltration (8,9); however this method presents a problem of membrane fouling.
- Removal of the anionic pollutants by floes, formed due to adsorption of Al 3+ onto the surface of lauryl sulfate (adsorptive micellar flocculation) was suggested by Porras-Rodriguez and Talens-Alesson (10). This method is efficient only for removal of anions, and it has limitations due to operational pH, which ranges from 2 to 3.5 and relatively high residual concentrations OfAl 3+ .
- the present invention is based on the finding that a combination of a granular material with a complex of micelles of an organic cation adsorbed on clay can efficiently adsorb anionic and neutral pollutants dissolved in contaminated water.
- the granular material is typically in excess to said complex.
- the present invention is directed to a method for purifying water from neutral or anionic pollutants present therein comprising contacting the polluted water with a mixture of (i) a granular material and (ii) a complex comprising micelles of organic cations adsorbed on clay.
- the ratio (w/w) between the granular material and said complex being in the range of about 5:1 to about 200:1, preferably about 50:1 to about 120:1 and most preferably about 75:1 to about 100: 1.
- water as used herein encompasses aqueous solutions.
- the aqueous solutions or “water” may be: water contaminated by industrial or domestic waste; affluent water; contaminated aqueous food products or raw material, e.g. contaminated milk, residual aqueous solution obtained after processing food, etc.
- water other than if accompanied by a descriptor thereof, will be used to refer to the contaminants/pollutants-containing water.
- purified water will be used to denote water that has been purified by the inventive method or system.
- present in the context of the invention refers to any manner in which pollutants or contaminants may appear in a liquid medium and includes solution, suspension, emulsion and presence as colloidal particles
- w/w means a ratio between the weight of one substance to that of another.
- a ratio (w/w) between the granular material and said complex of about 5:1 means that there are 5 weight units of the granular material for each 1 weight unit of said complex.
- Said contacting may be in a continuous flow process in which the water is flown through or over said mixture.
- at least one container containing said mixture is used.
- Said container may be a column containing said mixture through which the water is flown a rate such so as to permit the contaminants to be removed therefrom; or may be a pool, tank or reservoir into which the water is continuously introduced and continuously removed at a rate such that the mean residence time of the water in the container is sufficient to the contaminants to be removed therefrom.
- said contacting may be done in a batch-type procedure in which, for example, the polluted water is introduced into a container containing said mixture and incubated in said container for a time period sufficient for absorption of the pollutants from the water, whereupon it is removed.
- Such incubation may be with or without stirring or agitating the suspension of the water with said mixture.
- the invention is not limited to the physical manner in which the method is performed.
- the ratio of the organic cation and the clay is typically about 0.3:1 to about 0.7:1 (w/w), preferably about 0.4:1 to about 0.6:1, most preferably about 0.45:1 to about 0.5:1.
- a typical example of a container is a column accommodating said mixture.
- the column is entirely filled with said mixture.
- the column is partially filled with said mixture while other portions, typically at the column's bottom may be filled with another material or different mixture.
- one end of the column consisting about 7- 10% of the column's length comprises either the granular material or a mixture of granular material with clay.
- a plurality of columns may be employed, which may be all the same or may be different.
- granular material refers in particular to a material which is chemically inert, and which may be homogenous, or may be heterogeneous in size, chemical composition or structure.
- the granular material is preferably composed of particles having an average particles size from about 0.2mm to about 2mm.
- a preferred granular material is sand.
- Sand is any natural material resulting from disintegrated rocks, top soil or coastal soil, typically quartz-based sand.
- the clay may be any aggregate of hydrous silicate particles less than 4 ⁇ m in diameter consisting of a variety of phyllo silicate minerals rich in silicon, aluminium oxides and hydroxides which include variable amounts of structural water.
- the clay may be chosen from kaolinite-serpentine, illite, and smectite, preferably it is chosen from a smectite, most prefrably the clay is montmorillonite [(Na 5 Ca) 033 (Al 5 Mg) 2 Si 4 O 10 (OH) 2 -IiH 2 O].
- the organic cation is a cation having amphipatic properties which is capable of forming micelles in an aqueous medium.
- the tendency of the organic cation to form micelles in an aqueous medium can be enhanced by increasing the concentration of salts in the medium.
- the micelles are essentially spherical structures wherein the hydrophobic (organic) part of the organic cation is in its interior and the ionic part faces the aqueous medium.
- the micelles adsorbed on the clay may comprise each several different organic cations or the clay may have adsorbed thereon different types of micelles, each of which has a different composition of organic cations.
- Examples of preferred organic cations are: an ammonium cation of the type X + Y " wherein X + is an R"-N(R') 3 , R 1 being each independently a C 1-4 alkyl group, an optionally substituted phenyl or an alkylphenyl group; R" is C 12 -C 2 o-alkyl preferably C 14 -C 20 -alkyl, most preferably C 16 -C 2 o-alkyl and Y ' is a counter ion chosen from Cl “ , Br " or OH " ,.
- R is methyl, ethyl, propyl, pheny, benzyl and R" is C 14 H 29 , C 15 H 31 , C 16 H 33 , C 16 H 31 , C 17 H 35 , C 17 H 33 , C 18 H 37 , C 18 H 35 , C 19 H 39 C 19 H 37 , C 20 H 41 , C 20 H 39 '
- the ammonium cation is characterized as having a low critical micelle concentration (CMC) of less than ImM. Consequently, in the complex of an organic cation adsorbed on clay, the organic cation is adsorbed as a micelle.
- the pollutants which may be removed from water according to the invention are neutral or anionic organic pollutants.
- the neutral pollutants are selected from the group comprising of neutral herbicides or a halogenated C 1-8 moiety.
- the halogenated C 1-8 moiety is selected from Ci-shalogenoalkyls, C 1-8 halogenoalkenyls, Ci-shalogenoalkynyls which may be perlialogenated or their mixtures.
- the natural herbicides are selected from chloroacetamides, uracils or ureas.
- the herbicides are chosen from alachlor, acetochlor bromacil, chlorotoluron, chlorpropharm, chlorbromuron, dimefuron, diuron, fenuron, fluometuron, isoproturon, isouron, propachlor, dimethachlor, lenacyl, terbacil.
- the halogentated C 1-8 moieties are methyl, ethyl, ethenyl, ethynyl, propyl,, propenyl, propynyl, butyl, butylenyl, butynyl, pentyl, pentenyl, pentynyl hexyl, hexenyl, hexynyl comprising at least one halogen and may be also perlialogenated.
- the halogen is selected from F, Cl, Br, I.
- the anionic pollutants are selected from the group comprising of imidazolinones, triazolinones, sulfonylurea, aromatic carboxylic acids, liumic acid or fulvic acid, antibiotics or their mixtures.
- these are chosen from imazaquin, imazethapyr, imazapyr, imazamethabenz- methyl, imazamox, imazapic, chlorsulfuron, imazosulfuron, pyrazosulf ⁇ ron-ethyl, primisulfuron,-metliyl, nicosulfuron, bensulfuron-methyl, amicarbazone, azafenidin, sulfentrazone, sulfosulfuron.
- the antibiotics are tetracyclines, antibacterial such as sulfamethoxazole, sulfisoxazole, sulfamethizole, sulfazamet, sulfatolamide, sulfathiourea.
- the present invention is further directed to a system for carrying out the methods described above.
- the system intended for purifying water from neutral and/or anionic pollutants dissolved therein the system comprises at least one container adapted to receive the polluted water and containing a mixture of (i) a granular material and (ii) a complex comprising micelles of an organic cation adsorbed on clay.
- a body of water including, for example, open water pools or reservoirs, water contained in tanks, etc.
- introducing into the water i) the micelles of the organic cations and then introducing particulate clay, e.g. of the kind specified above, or (ii) the complex of the micelles with the clay.
- particulate clay e.g. of the kind specified above
- the complexes of the micelles and the clay are formed in situ. Said complexes may then be permitted to sediment and the sediment may then be collected.
- the present invention also provides a method for purifying water, comprising: adding into the water (i) micelles of an organic cation and particulate clay, typically first the micelles and subsequently the particulate clay, or (ii) a complex of micelles of an organic cation adsorbed on clay. In the former case a complex between the particulate clay and the micelles is formed in situ.
- the clay-micelles complex is permitted to sediment and the sediment is then collected.
- the sedimentation may be a free, gravity-induced sedimentation or may be a forced one, e.g. using a centrifuge.
- the micelles or said complex are typically incubated for a time period allowing the micelles to absorb the pollutants from the water. During such an incubation stage, the water may be stirred or agitated so as to improve the rate and/or efficiency of absorption. Where the micelles and the particulate clay are introduced separately, there may be an incubation period occurring prior to the introduction of the particulate clay.
- the micelles and the clay will typically be introduced in the water in the form of an aqueous suspension.
- a micelle formulation, the particulate clay and a formulation comprising said complex may originally be in a dry or lyophilized form.
- Fig. 1 shows the chemical structures of two organic cations forming micelles for capturing organic pollutants and several neutral pollutants.
- Fig. 2 shows the chemical structure of the tetracycline family; (B) the various substituents in the tetracycline family; (C) chemical structure and dissociation constants of several antibacterials.
- Figs. 3(A)-(E) show the isotherms of adsorption of (A) acetochlor, (B) imazaquine, (C) bromacil, (D) alachlor, (E) chlorotoluron, on micelle-clay complexes.
- Diamonds and squares correspond to BDMHD A-clay; triangles and circles correspond to ODTMA-clay; squares and circles (dash line) show the calculated values.
- the present invention is directed to a method and system for purifying water from neutral and/or anionic pollutants present therein.
- Use is made a mixture of a granular material and a complex comprised of micelles of organic cation adsorbed on clay which may contained in a container.
- the invention is not limited to the use of a container and it is possible, for example, to introduce said mixture into water reservoirs for in situ water purification.
- the container is preferably in the form of a column where the system may be formed of a single column or comprise a two or more columns connected in series or in parallel by channels, pipes or any conduit enabling the flow (by gravity or by forced pumping) of water between them .
- column is a preferred container type according to the invention, the invention is not limited thereto and other container types may be used.
- These include containers adapted for a batch-type purification process, such as open pools or basins, tanks, etc., with or without a water stirrer or agitator. For purification the water is introduced and the removed after a time sufficient for removal of the pollutants form the water by said mixture.
- containers for a flow-based purification process in which the liquid is flown through or over said mixture, including columns, flow-through reservoirs or pools with inlet at one or more points and outlet at one or more other points situated such so as to ensure flow of water through or over said mixture in manner to permit removal of the contaminants from the water.
- Columns may either be fully filled with said mixture or the column may comprise also layers filled with a different composition.
- the layer filled with a different composition may, for example, be a thin layer at one end, e.g. its bottom, the width of such layer being about 7-10% of the length of the column, said layer comprising only the granular material or a mixture of the granular material and clay (without the organic cation ) .
- the column may have alternate first and second types of layers, which may be of the same or different thicknesses, wherein the first layers contain said mixture and the second layers comprising of a different composition.
- Micelle-clay complexes are known and used in the removal of anionic organic molecules from water, (11-14).
- the micelle-clay complexes is prepared first and dried (14).
- the organic cation/clay complex is optimized by a selection of preferred organic cations which form an organic cation/clay complex where the organic cation is in the form of a micelle.
- the optimized complex is mixed with a granular material, preferably sand, yielding an efficient combination for purification of a variety of contaminants from water.
- the optimized micelle-clay system alone is also powerful in the removal of neutral molecules from water, as shown in Tables 1 to 5, although the combined system comprising the mixture yields far better purification of water from dissolved contaminants.
- Optimization of the removal of neutral pollutants from water requires a optimization of the structurally compatible organic cations composing the micelles, those having a long alkyl chain and having a low critical micelle concentration (CMC).
- CMC critical micelle concentration
- a concentrated solution (several mM) of organic cations is prepared, where the cations include a large hydrophobic part and consequently have the desired very low CMC.
- Such cations are octadecyltrimethylammonium (ODTMA) which has an alkyl chain of 18 carbon atoms and a CMC of 0.3 mM (11), or benzyldimethylhexadecilammonium (BDMHDA) which has an alkyl chain of 16 carbon atoms and a CMC of 0.6 mM (15) (Fig. 1 for their structural formulae).
- OTMA octadecyltrimethylammonium
- BDMHDA benzyldimethylhexadecilammonium
- micelle-clay systems of the present invention remove from contaminated water 99% of the anionic herbicides sulfentrazone and sulfosulfuron for a suspension of less than 1% (w/w) micelle-clay, and 99.5%, 97%, 93% and 95% of the neutral herbicides bromacil, alachlor, acetochlor and chlorotoluron (Fig. 1 for structural formulae of these neutral contaminants) in a suspension containing montmorillonite at 10g/L.
- Adsorption of pollutants depended on the micelle-clay ratio as shown in Tables 3 and 4. Maximal adsorption of the anionic imazaquin as well as the neutral alachlor in these experiments was obtained by using 2.5mM of BDMHDA and 2g/L clay. Increasing the concentrations of BDMHDA at the same clay concentration, resulted in a reduction in the amounts of adsorbed herbicides. The explanation is that herbicides bound to the micelles remained in the supernatant solution, due to reduced fraction of the adsorbed micelles, which were in excess relative to the available clay sites.
- Table 6 also includes for comparison, for several pollutants, the percentage values of removal by a filter filled with activated carbon mixed with sand.
- the results indicate that the filter based on the sand/micelle-clay complex is much more efficient than the one containing activated carbon one.
- 98% removal (by micelle-clay) vs. 58% removal by activated carbon (Table 6, 23 cm length of filter) implies that the fractions of pollutants remaining in solution would be 0.0004 and 0.18, respectively, for a filter whose length is doubled (46 cm), i.e., 450-fold less pollutant would remain in solution for filtration by micelle-clay than by activated carbon.
- Similar results for the efficiencies of removal were obtained in the presence of fulvic acid or humic acid (Table 7).
- the organic cations employed in the micelle-clay complexes have high affinity for adsorption on montmorillonite (11, 15). Thus any released cations can be completely captured by quartz-clay layer.
- the results of the present invention demonstrate that the micelle-clay system is efficient for the removal of contaminants from water in the range of milligrams to micrograms per liter. Thus more than 99% removal of organic pollutants was achieved by passage of a solution through a 22 cm layer of quartz mixed with micelle-clay at 100/1 ratio. The implication is that there will be seven to eight orders of magnitude reduction in the concentrations of these pollutants for four passages through similar columns or for one passage through a 1 meter column.
- a carbon analysis was done measuring the amount of the released organic cation from micelle-clay complexes in column-filters for water purification after adding a layer (10cm) of quartz mixed with clay (150:1 w/w) at the bottom of the column. Separate measurements which determined the carbon released from columns filled with quartz or with quartz/clay mixtures are presented in Table 8 (17).
- the measurements of the Dissolved organic carbon (DOC) showed that the carbon concentration in the filtered water due to the organic cation released from the micelle-clay complexes (0.2 ppm) was less than (or equal within the experimental error) the carbon concentration in the water filtered through the quartz or the quartz- clay mixture.
- the carbon analysis showed that in the ppm range all the released cations (ODTMA or BDMHDA) were retained by the column-filter, i.e., by the 10 cm layer of quartz mixed with clay.
- the water which eluted or passed through a column filled with quartz mixed with micelle/clay was also passed three times through a 25 cm column filled with quartz-clay (150:1 w/w) and then concentrated 1000-fold.
- Measurements with GC-MS showed that the concentration of organic cation in the eluate was less than 1 ppb.
- Table 9 gives capacities of the micelle-clay filter for removal of several pollutants. The results are expressed as percent (W/W) of the total captured pollutant relative to the weight of the micelle, which is included in the filter (2gr). This presentation reflects the fact that the other components in the filter, i.e., sand and clay are much cheaper than the organic cation. The (W/W) percent values varied from 12.7 to 37. Table 9
- Capacity of the micelle-clay filter for several pollutants expressed as percent (w/w) of pollutant relative to the organic cation.
- the clay used was Wyoming Na-montmorillonite SWy-2 obtained from the Source Clays Repository (Clay Minerals Society, Columbia, MO). Quartz sand (grain size 0.8-1.5 mm) was purchased from Negev Industrial Minerals (Israel). Octadecyltrimethylammonium bromide (ODTMA) was purchased from Sigma- Aldrich (Sigma Chemical Co., St. Louis, MO). Benzyldimethylhexadecylammonium chloride (BDMHDA) was purchased from Fluka Chemie (Buchs, Switzerland). Technical sulfentrazone (purity 91.3%) was obtained from FMC (Princeton, NJ); sulfosulfuron (analytical grade) was obtained from E. I.
- Du Pont de Nemours and Company (Wilmington, DE). Acetochlor, alachlor, imazaquin, and chlorotoluron (all compounds of 98% purity) were supplied by Agan Makhteshim, Israel. Benzoic acid was purchased from Merck (Darmstadt, Germany). Tetracycline hydrochloride, oxytetracycline hydrochloride, chlortetracycline hydrochloride, sulfamethoxazole, sulfisoxazole, and sulfamethizole were purchased from Sigma-Aldrich or Fluka (Switzerland). Structural formulae of surfactants are shown on Figure 1. Seeds of sorghum ⁇ Sorghum bicolor (L.)) from Hazera, (Israel) were used for bioassay tests.
- ODTMA and BDMHDA were added to the solutions of pollutants. Pollutant-micelle complexes were kept stirring for 72 h. Then 10 ml of micelle-pollutant complexes were mixed in a polypropylene copolymer centrifuge tube with 5ml of water suspension of montmorillonite. Preliminary experiments showed -no adsorption of pollutants on the tubes. Concentrations of surfactants in suspensions were 2.5; 5 and 12 niM, i.e., much above their CMC values, which are 0.3 mM and 0.6 niM for ODTMA and BDMHDA, respectively (11, 15). Concentrations of pollutants in suspensions were in the range from 1.33 mg/L to 33.3 mg/L; lower concentrations of 0.16 and 0.005mg/L were also used for acetochlor and alachlor, respectively.
- Concentrations of micelle-clay complexes were 2, 5 and 10 g /L. Tubes containing suspensions of pollutants and micelle-clay complexes were kept at 25+1 ° C under continuous agitation for 72 h. Then the tubes were centrifuged for 20 min. at 15000 g and supernatants were passed through teflon filters (ISI, Israel) of 0.2 ⁇ m pore diameter and analyzed.
- teflon filters ISI, Israel
- Desorption Desorption of imazaquin and acetochlor was studied from BDMHD A-clay complex, which was obtained in adsorption experiments at 2.5 mM BDMHDA, 3 g L "1 clay with herbicides. After removing the supernatants 0.045 g of herbicide-micelle-clay complexes were mixed in centrifuge tubes with 15 ml of distilled water; the final complex concentrations were 3g L "1 . Tubes were kept at 25+1 0 C under continuous agitation for 1 or 7 days. Then the tubes were centrifuged for 20 min. at 15000 g and concentrations of herbicides in supernatants were measured. Adsorption and desorption experiments were performed in triplicate. Desorption of bromacil was studied from from BDMHDA-clay complex, which was obtained in adsorption experiments at 12 mM BDMHDA, 1Og L "1 clay with herbicide. Adsorption and desorption experiments were performed in triplicate.
- Non woven polypropylene geo textile filters (Markham Culverts Ltd., Papua New Guinea) were placed on both sides of the column.
- the column was connected to a peristaltic pump and saturated by distilled water from the bottom (flow 2 or 5 ml/min).
- flow 2 or 5 ml/min flow 2 or 5 ml/min.
- sulfosulfuron tests indicated that the same outcome was obtained for flow rates between 2 and 20 ml/min. Estimates indicate that the flow rates can be further increased.
- HPLC column for herbicides was LiChrospher R 100 RP- 18 (5 ⁇ M) and the flow rate was 1.0 mL min "1 .
- anionic pollutants the binary mixtures of organic solvent (acetonitrile or methanol) with water acidified by trifmoroacetic acid to pH 2.95+0.09 were used as mobile phases: acetonitrile/water (50/50) for sulfentrazone; acetonitrile/water (70/30) for sulfosulfuron; methanol/water (60/40) for imazaquin and benzoic acid.
- acetonitrile/water 70/30
- acetochlor and alachlor methanol/water (75/25) for chlorotoluron
- methanol/water methanol/water (65/35) for bromacil.
- concentrations -of pollutants were measured at the following wavelengths: sulfentrazone at 220 nm, sulfusulfuron at 216 nm, imazaquin at 242nm, benzoic acid at 228 nm, acetochlor and alachlor at 216 nm, chlorotoluron at 248 nm, and bromacil at 280 nm.
- the sample was extracted by solid- phase extraction using 3M Empore TM SDS-RPS (47 mm) extraction discs (Varian, CA, USA) and vacuum manifold. Disc was consecutively conditioned with 5 ml and 15 ml of acetonitrile followed by drying under the vacuum after each step of conditioning. Then next 15 ml of acetonitrile was added followed by 15 ml of double-distilled water. One liter of sample was passed through the conditioned disc. Sulfamethizole was consecutively eluted three times by 5 ml of acetonitrile followed by 5 ml of methanol.
- GC-MS measurements were performed with (TermoQuest GC Trace2000 Polaris Instrument) fitted with DB-5.MS capillary column, 30m * 0.25mm i.d. x 0.25 ⁇ m film thickness from J&W Scientific (CA, USA)
- the carrier gas was helium (linear velocity was 33cm/s).
- Injector temperature was 25O 0 C.
- the oven temperature was held at 45 0 C for 2min, then raised at 40°C/min to 16O 0 C, followed by 5°C/min to 21O 0 C and finally raised at 40°C/min up to 28O 0 C.
- the transfer line temperature was 295 0 C. Phenantren D 10 was used as internal standard.
- Solutions containing different concentration of sulfosulfuron were added to the dishes (15 ml per dish) to check dose-response of sorghum for the herbicide and to obtain a calibration curve as reported in (18).
- the eluate from the column was added to Petri dishes.
- Four replicas were performed for each concentration and for eluate.
- Sorghum seeds were planted in the sand 1 cm from the bottom of each dish. After sowing, the dishes were sealed and incubated in a dark room at 28° C tilted face up at 80° angles. The root lengths were measured after 3 days of incubation.
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Abstract
There is provided a method or a system for purification of water from neutral and anionic organic contaminants using either a mixture of a complex of an organic cation adsorbed on clay as a micelle, and a granular material or a complex of an organic cation adsorbed on clay as a micelle. There is also provided a column accommodating the mixture of a complex of an organic cation adsorbed on clay as a micelle, and a granular material.
Description
REMOVAL OF ORGANIC POLLUTANTS FROM CONTAMINATED WATER
FIELD OF THE INVENTION
This invention relates to systems for removal of organic pollutants from water.
BACKGROUND OF THE INVENTION
In the text below reference is made to prior ait documents, listed at the end of the description before the claims. These prior art documents are relevant for understanding the state of the art in the field of the invention. The reference will be referred to in the text by giving their serial number from said list.
Pollution of groundwater and wells has become an environmental and economical hazard due to intensively irrigated agriculture and application of herbicides and pesticides over cultivated lands as well as waste spills within the catchments areas of the various hydrogeological basins (1).
Conventional treatment techniques such as sand filtration, sedimentation, flocculation, coagulation, chlorination and activated carbon are not effective in reducing the concentration of the organic pollutants in the presence of dissolved organic matter
(2).
The adsorption of organic cations on clays transforms the clay-mineral surface from hydrophilic to hydrophobic, enhancing its affinity for sorbing neutral organic molecules of hydrophobic characteristics (3, 4), rendering it suitable for removing organic pollutants from water. When the loading of the organic cations exceeds the cation exchange capacity (CEC) of the clay, it becomes positively charged and potentially suitable for the adsorption of certain anions, such as imazaquin (5). Organo- clays are widely used in wastewater treatment. Still the quality of water, which can be used for drinking, has to be improved.
Solubilization of organic pollutants by micelles of surfactants (6, 7) was the basis of the micellar-enhanced ultrafiltration (8,9); however this method presents a problem of membrane fouling. Removal of the anionic pollutants by floes, formed due to adsorption of Al3+ onto the surface of lauryl sulfate (adsorptive micellar flocculation)
was suggested by Porras-Rodriguez and Talens-Alesson (10). This method is efficient only for removal of anions, and it has limitations due to operational pH, which ranges from 2 to 3.5 and relatively high residual concentrations OfAl3+.
SUMMARY OF THE INVENTION
The present invention is based on the finding that a combination of a granular material with a complex of micelles of an organic cation adsorbed on clay can efficiently adsorb anionic and neutral pollutants dissolved in contaminated water. The granular material is typically in excess to said complex.
In the following, numerical values that are given should be understood as being approximations and represent a value with the range of 70% to 130% of the one indicated. Thus, for example, "0.2 mm" refers in fact to 0.14 - 0.26 mm.
Thus the present invention is directed to a method for purifying water from neutral or anionic pollutants present therein comprising contacting the polluted water with a mixture of (i) a granular material and (ii) a complex comprising micelles of organic cations adsorbed on clay.
According to one embodiment, the ratio (w/w) between the granular material and said complex being in the range of about 5:1 to about 200:1, preferably about 50:1 to about 120:1 and most preferably about 75:1 to about 100: 1.
The term "water" as used herein encompasses aqueous solutions. The aqueous solutions or "water" may be: water contaminated by industrial or domestic waste; affluent water; contaminated aqueous food products or raw material, e.g. contaminated milk, residual aqueous solution obtained after processing food, etc.
The term "water", other than if accompanied by a descriptor thereof, will be used to refer to the contaminants/pollutants-containing water. The term "purified water" will be used to denote water that has been purified by the inventive method or system.
The term "present" in the context of the invention refers to any manner in which pollutants or contaminants may appear in a liquid medium and includes solution, suspension, emulsion and presence as colloidal particles
In the description herein the terms "pollutants" and "contaminants" will be used interchangeably.
The term (w/w) means a ratio between the weight of one substance to that of another. Thus, a ratio (w/w) between the granular material and said complex of about 5:1 means that there are 5 weight units of the granular material for each 1 weight unit of said complex.
Said contacting may be in a continuous flow process in which the water is flown through or over said mixture. For that purpose at least one container containing said mixture is used. Said container may be a column containing said mixture through which the water is flown a rate such so as to permit the contaminants to be removed therefrom; or may be a pool, tank or reservoir into which the water is continuously introduced and continuously removed at a rate such that the mean residence time of the water in the container is sufficient to the contaminants to be removed therefrom.
Alternatively said contacting may be done in a batch-type procedure in which, for example, the polluted water is introduced into a container containing said mixture and incubated in said container for a time period sufficient for absorption of the pollutants from the water, whereupon it is removed. Such incubation may be with or without stirring or agitating the suspension of the water with said mixture.
In addition, it is possible also to introduce said mixture into reservoirs containing said water for an in situ purification.
Generally, the invention is not limited to the physical manner in which the method is performed.
The ratio of the organic cation and the clay is typically about 0.3:1 to about 0.7:1 (w/w), preferably about 0.4:1 to about 0.6:1, most preferably about 0.45:1 to about 0.5:1.
As noted above, a typical example of a container is a column accommodating said mixture. By one embodiment the column is entirely filled with said mixture. In accordance with another embodiment, the column is partially filled with said mixture while other portions, typically at the column's bottom may be filled with another material or different mixture. For example, one end of the column consisting about 7- 10% of the column's length comprises either the granular material or a mixture of granular material with clay. It is also possible to prepare a column having alternate first and second types of layers, wherein the first layers contain said mixture and the second layers another material or different mixtures. A plurality of columns may be employed, which may be all the same or may be different.
- A -
The term "granular material" refers in particular to a material which is chemically inert, and which may be homogenous, or may be heterogeneous in size, chemical composition or structure.
The granular material is preferably composed of particles having an average particles size from about 0.2mm to about 2mm. A preferred granular material is sand. Sand is any natural material resulting from disintegrated rocks, top soil or coastal soil, typically quartz-based sand.
The clay may be any aggregate of hydrous silicate particles less than 4μm in diameter consisting of a variety of phyllo silicate minerals rich in silicon, aluminium oxides and hydroxides which include variable amounts of structural water. The clay may be chosen from kaolinite-serpentine, illite, and smectite, preferably it is chosen from a smectite, most prefrably the clay is montmorillonite [(Na5Ca)033(Al5Mg)2Si4O10(OH)2-IiH2O].
The organic cation is a cation having amphipatic properties which is capable of forming micelles in an aqueous medium. The tendency of the organic cation to form micelles in an aqueous medium can be enhanced by increasing the concentration of salts in the medium. The micelles are essentially spherical structures wherein the hydrophobic (organic) part of the organic cation is in its interior and the ionic part faces the aqueous medium. The micelles adsorbed on the clay may comprise each several different organic cations or the clay may have adsorbed thereon different types of micelles, each of which has a different composition of organic cations.
Examples of preferred organic cations are: an ammonium cation of the type X+Y" wherein X+ is an R"-N(R')3, R1 being each independently a C1-4alkyl group, an optionally substituted phenyl or an alkylphenyl group; R" is C12-C2o-alkyl preferably C14-C20-alkyl, most preferably C16-C2o-alkyl and Y' is a counter ion chosen from Cl", Br" or OH",. Preferably, R is methyl, ethyl, propyl, pheny, benzyl and R" is C14H29, C15H31, C16H33, C16H31, C17H35, C17H33, C18H37, C18H35, C19H39 C19H37, C20H41, C20H39 ' The ammonium cation is characterized as having a low critical micelle concentration (CMC) of less than ImM. Consequently, in the complex of an organic cation adsorbed on clay, the organic cation is adsorbed as a micelle.
The pollutants which may be removed from water according to the invention are neutral or anionic organic pollutants. The neutral pollutants are selected from the group comprising of neutral herbicides or a halogenated C1-8 moiety. The halogenated C1-8
moiety is selected from Ci-shalogenoalkyls, C1-8halogenoalkenyls, Ci-shalogenoalkynyls which may be perlialogenated or their mixtures. The natural herbicides are selected from chloroacetamides, uracils or ureas. In particular, the herbicides are chosen from alachlor, acetochlor bromacil, chlorotoluron, chlorpropharm, chlorbromuron, dimefuron, diuron, fenuron, fluometuron, isoproturon, isouron, propachlor, dimethachlor, lenacyl, terbacil. The halogentated C1-8 moieties are methyl, ethyl, ethenyl, ethynyl, propyl,, propenyl, propynyl, butyl, butylenyl, butynyl, pentyl, pentenyl, pentynyl hexyl, hexenyl, hexynyl comprising at least one halogen and may be also perlialogenated. The halogen is selected from F, Cl, Br, I. The anionic pollutants are selected from the group comprising of imidazolinones, triazolinones, sulfonylurea, aromatic carboxylic acids, liumic acid or fulvic acid, antibiotics or their mixtures. In particular these are chosen from imazaquin, imazethapyr, imazapyr, imazamethabenz- methyl, imazamox, imazapic, chlorsulfuron, imazosulfuron, pyrazosulfαron-ethyl, primisulfuron,-metliyl, nicosulfuron, bensulfuron-methyl, amicarbazone, azafenidin, sulfentrazone, sulfosulfuron. The antibiotics are tetracyclines, antibacterial such as sulfamethoxazole, sulfisoxazole, sulfamethizole, sulfazamet, sulfatolamide, sulfathiourea.
The present invention is further directed to a system for carrying out the methods described above. The system according to a preferred embodiment, intended for purifying water from neutral and/or anionic pollutants dissolved therein the system comprises at least one container adapted to receive the polluted water and containing a mixture of (i) a granular material and (ii) a complex comprising micelles of an organic cation adsorbed on clay.
In accordance with the invention that it is possible also to purify a body of water, including, for example, open water pools or reservoirs, water contained in tanks, etc., by introducing into the water (i) the micelles of the organic cations and then introducing particulate clay, e.g. of the kind specified above, or (ii) the complex of the micelles with the clay. In the former case (that under (i)) the complexes of the micelles and the clay are formed in situ. Said complexes may then be permitted to sediment and the sediment may then be collected.
Thus, the present invention also provides a method for purifying water, comprising: adding into the water (i) micelles of an organic cation and particulate clay, typically first the micelles and subsequently the particulate clay, or (ii) a complex of
micelles of an organic cation adsorbed on clay. In the former case a complex between the particulate clay and the micelles is formed in situ.
By one embodiment, after an incubation period the clay-micelles complex is permitted to sediment and the sediment is then collected. The sedimentation may be a free, gravity-induced sedimentation or may be a forced one, e.g. using a centrifuge.
After the addition of the micelles followed by the addition of particulate clay or after the introduction of said complex, as the case may be, the micelles or said complex are typically incubated for a time period allowing the micelles to absorb the pollutants from the water. During such an incubation stage, the water may be stirred or agitated so as to improve the rate and/or efficiency of absorption. Where the micelles and the particulate clay are introduced separately, there may be an incubation period occurring prior to the introduction of the particulate clay.
The micelles and the clay will typically be introduced in the water in the form of an aqueous suspension. A micelle formulation, the particulate clay and a formulation comprising said complex, may originally be in a dry or lyophilized form.
BRIEF DESCRIPTION OF THE DRAWINGS
In order to understand the invention and to see how it may be carried out in practice, a preferred embodiment will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:
Fig. 1 shows the chemical structures of two organic cations forming micelles for capturing organic pollutants and several neutral pollutants.
Fig. 2 (A) shows the chemical structure of the tetracycline family; (B) the various substituents in the tetracycline family; (C) chemical structure and dissociation constants of several antibacterials.
Figs. 3(A)-(E) show the isotherms of adsorption of (A) acetochlor, (B) imazaquine, (C) bromacil, (D) alachlor, (E) chlorotoluron, on micelle-clay complexes. Diamonds and squares correspond to BDMHD A-clay; triangles and circles correspond to ODTMA-clay; squares and circles (dash line) show the calculated values.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
As mentioned the present invention is directed to a method and system for purifying water from neutral and/or anionic pollutants present therein. Use is made a
mixture of a granular material and a complex comprised of micelles of organic cation adsorbed on clay which may contained in a container. As already pointed out above, the invention is not limited to the use of a container and it is possible, for example, to introduce said mixture into water reservoirs for in situ water purification.
The container is preferably in the form of a column where the system may be formed of a single column or comprise a two or more columns connected in series or in parallel by channels, pipes or any conduit enabling the flow (by gravity or by forced pumping) of water between them . While column is a preferred container type according to the invention, the invention is not limited thereto and other container types may be used. These include containers adapted for a batch-type purification process, such as open pools or basins, tanks, etc., with or without a water stirrer or agitator. For purification the water is introduced and the removed after a time sufficient for removal of the pollutants form the water by said mixture. These also include containers for a flow-based purification process in which the liquid is flown through or over said mixture, including columns, flow-through reservoirs or pools with inlet at one or more points and outlet at one or more other points situated such so as to ensure flow of water through or over said mixture in manner to permit removal of the contaminants from the water.
Columns may either be fully filled with said mixture or the column may comprise also layers filled with a different composition. The layer filled with a different composition may, for example, be a thin layer at one end, e.g. its bottom, the width of such layer being about 7-10% of the length of the column, said layer comprising only the granular material or a mixture of the granular material and clay (without the organic cation ) . It is also possible, by some embodiments of the invention, for the column to have alternate first and second types of layers, which may be of the same or different thicknesses, wherein the first layers contain said mixture and the second layers comprising of a different composition.
Micelle-clay complexes are known and used in the removal of anionic organic molecules from water, (11-14). For efficient use of the micelle-clay complexes as a filter for contaminants, the micelle-clay is prepared first and dried (14). According to the present invention the organic cation/clay complex is optimized by a selection of preferred organic cations which form an organic cation/clay complex where the organic cation is in the form of a micelle. In addition, the optimized complex is mixed with a
granular material, preferably sand, yielding an efficient combination for purification of a variety of contaminants from water. According to the present invention, the optimized micelle-clay system alone is also powerful in the removal of neutral molecules from water, as shown in Tables 1 to 5, although the combined system comprising the mixture yields far better purification of water from dissolved contaminants. Optimization of the removal of neutral pollutants from water requires a optimization of the structurally compatible organic cations composing the micelles, those having a long alkyl chain and having a low critical micelle concentration (CMC). A concentrated solution (several mM) of organic cations is prepared, where the cations include a large hydrophobic part and consequently have the desired very low CMC. Such cations are octadecyltrimethylammonium (ODTMA) which has an alkyl chain of 18 carbon atoms and a CMC of 0.3 mM (11), or benzyldimethylhexadecilammonium (BDMHDA) which has an alkyl chain of 16 carbon atoms and a CMC of 0.6 mM (15) (Fig. 1 for their structural formulae). The anionic and neutral organic pollutants bind well to the positively charged micelles, which attract electrostatically their negatively-charged moieties. Furthermore, the interior parts of the micelles provide a hydrophobic environment for the organic molecules. The micelles with incorporated pollutants, which carry a net positive charge, adsorb on negatively charged clay platelets, e.g., montmorillonite.
Turning to Table IA it is demonstrated that micelle-clay systems of the present invention remove from contaminated water 99% of the anionic herbicides sulfentrazone and sulfosulfuron for a suspension of less than 1% (w/w) micelle-clay, and 99.5%, 97%, 93% and 95% of the neutral herbicides bromacil, alachlor, acetochlor and chlorotoluron (Fig. 1 for structural formulae of these neutral contaminants) in a suspension containing montmorillonite at 10g/L.
Turning to the anionic pollutants, imazaquin, and benzoic acid, and the neutral pollutants, e.g. herbicides, such as chlorotoluron (Table IA), the results indicate that the nature of the headgroup of the organic cation which forms the micelle may be critical; compatibility of the aromatic head group of BDMHDA with the aromatic structure of pollutant molecules led to a significant increase in the sorption of these pollutants. Thus 92% removal of imazaquin was obtained by using BDMHDA, whose headgroup includes an aromatic group and shows some structural similarity to that of imazaquin, whereas ODTMA micelles only yielded 73% removal of imazaquin. Removal of
benzoic acid by BDMHD A-clay was 91% versus 61% by ODTMA-clay. A similar preference is observed with the neutral molecules acetochlor and chlorotoluron, which also include an aromatic ring. The importance of interactions between the phenyl rings of certain herbicides and those of organic cations was previously suggested for several hydrophobic herbicides interacting with organo-clays {16). In the present invention, the removal of chlorotoluron by the complex of the invention was enhanced by BDMHDA- clay as compared with ODTMA-clay as shown in (Table IA). The addition of the dry micelle-clay complex to water containing the pollutants yielded similar or slightly smaller percentages of pollutant removal. Turning to Table IB it is demonstrated that the micelle-clay/sand system of the present invention is also efficient in the removal of antibiotics such as tetracycline and oxytetracycline (Figs. 2(A) and 2(B) for their structural formulae) from water.
Table IA
Removal of organic molecules from water by ODTMA-clay and BDMHD A-clay complexes
Initial and final concentrations were analyzed by GC-MS. The standard deviations obtained for adsorption ranged between 3 and 6 %.
Table IB
Water purification from antibiotics by micelle-montmorillonite complexes in suspension (12mM BDMHDA, 10g/I clay)
Contaminant Initial cone, % removed mg/L
Tetracycline 6.67 92
Oxytetracycline 6.67 99.8
Sulfamethizole 6.67 99
Sulfamethoxazole 6.67 96.5
Sulfisoxazole 6.67 96.7
The adsorption isotherms of neutral herbicides are almost linear, as in their partition profile. Analysis by Langmuir equation as described (16) yielded good fits as demonstrated in Figs. 3(A)-(E) and further in Table 2. Isotherms of adsorption of the anionic pollutant imazaquin are less linear on BDMHD A-clay and ODTMA-clay. This pattern might reflect the decrease of the positive surface potential of micelles in the presence of larger concentrations of the anionic pollutants.
Table 2 Analysis of sorption efficacy of micelle-clay complexes by Langmuir equation.
BDMHDA-clay ODTMA-clay
Pollutant
BDMHDA-clay ODTMA-clay
Pollutant
K R2 RMSE K R2 RMSB
(tnmol/g) (M-1) (mmol/g)
Chlorotoiuron 2500 1 1.9XlO"5 500 1 8.4xlO"5
Acetochlor 2000 0.999 9.5XlO'5 1500 0.999 1.14XlO"4
Alachlor 3000 1 3.5X10"5 Nda Nda Nda
Bromacil 10000 1 2XlO-5 NcP Nda Nda
a Not determined. b RMSE = (∑ Oeχp i - ycakj f /(« - 1)}0'5 s Jn which yexp ,- and y oa,c { are i=l experimental and calculated adsorbed values, and n is the number of experimental points. cThe estimated uncertainties in k-values were 10-30%; in the case of bromacil the uncertainty was 50%.
Adsorption of pollutants depended on the micelle-clay ratio as shown in Tables 3 and 4. Maximal adsorption of the anionic imazaquin as well as the neutral alachlor in these experiments was obtained by using 2.5mM of BDMHDA and 2g/L clay. Increasing the concentrations of BDMHDA at the same clay concentration, resulted in a reduction in the amounts of adsorbed herbicides. The explanation is that herbicides bound to the micelles remained in the supernatant solution, due to reduced fraction of the adsorbed micelles, which were in excess relative to the available clay sites.
Table 3
Adsorption of imazaquin on BDMHD A-montmorillonite complexes at different micelle-clay ratios.
Table 4 Adsorption of acetochlor on BDMHD A-montmorillonite complexes
When the clay concentration increased for a fixed concentration of organic cation, the adsorption of herbicides decreased. In this case adsorption of BDMHDA monomers on excess clay resulted in decomposition of micelles to monomers. The adsorption of imazaquin and acetochlor on the monomer-clay complexes was significantly lower than that on the micelle-clay complexes as was previously found for sulfometuron {11), sulfentrazone (13) and alizarinate (15). These results demonstrate
that efficient removal of pollutants from water by means of the micelle-clay system requires an optimization of the micelle-clay ratio.
Desorption of imazaquin and acetochlor from BDMHD A-clay complex after 24 h was around 7% for 0.3% (w/w) suspension. Desorption decreased after 7 days to 2% for imazaquin. Desorption of acetochlor was 4-7% (Table 5). The interpretation ■ of these results is that loosely adsorbed molecules of herbicides were easily released, but then re-adsorbed. Low degree of desorption from ODTMA-montmorillonite complexes was also found for the anionic herbicides sulfometuron and sulfentrazone (11, 13). Desorption of bromacil from l%(w/w) suspension was less than 1% in the range of adsorbed amounts from 0.19 to 4.98 mg/g.
Table 5
Desorption of imazaquin and acetochlor from BDMHD A-montmorillonite complexes (3g/L)
aNot determined. The standard deviation obtained for desorption ranged between 0.5 and 3%.
Tuming to the at least one column filled with the mixture of (i) a granular material and (ii) a complex of organic cation adsorbed on clay as a micelle (hereinafter Column filters), the efficacy of column filters containing a mixture of quartz sand and BDMHDA micelle-clay complex at 100:1 w/w ratio for removal of pollutants from water is shown in Table 6. More than 99% of sulfentrazone, sulfosulfuron, imazaquine, alachlor, acetochlor and chlorotoluron were removed from the solutions of 10mg/L; 97% of alachlor was removed from the solution of 0.005mg/L.
The efficacy of column filters (25 cm length; diameter 5 cm) containing a mixture of quartz sand and BDMHDA micelle-clay complex at 100:1 (w/w) ratio (23 cm followed by a layer of 2 cm quartz sand) for removal of pollutants from water is shown in Table 6. More than 99% of sulfentrazone, alachlor, chlorotoluron and sulfosulfuron were removed from the solutions of 10mg/L; 97% of alachlor was removed from the solution of 0.005 mg/L. Removal of ethylene dibromide was 92.5%.
Table 6 also includes for comparison, for several pollutants, the percentage values of removal by a filter filled with activated carbon mixed with sand. The results indicate that the filter based on the sand/micelle-clay complex is much more efficient than the one containing activated carbon one. It is to be noted that 98% removal (by micelle-clay) vs. 58% removal by activated carbon (Table 6, 23 cm length of filter) implies that the fractions of pollutants remaining in solution would be 0.0004 and 0.18, respectively, for a filter whose length is doubled (46 cm), i.e., 450-fold less pollutant would remain in solution for filtration by micelle-clay than by activated carbon. Similar results for the efficiencies of removal were obtained in the presence of fulvic acid or humic acid (Table 7).
The initial concentration of the sulfosulfuron solution, which was passed through the column filter, was 200 μg/L. Hence, 99.5% of initial amount of sulfosulfuron was retained by the column filter (Table 6). Thus, results of the bioassay with small concentrations of sulfosulfuron confirmed the results of experiments with larger concentrations of herbicide, which were measured by HPLC.
Table 6
Removal of organic molecules from water by a column filter containing a mixture of quartz sand and BDMHDA micelle-clay at a 100/1 ratio (w/w) and a comparison to a filter filled with activated carbon (in parenthesis)
Solutions were passed through column filter containing a mixture of quartz sand and micelle-clay at a 100:1 ratio (w/w) and then through 3 sequential columns with quartz sand and clay at 150:1 ratio to remove residual organic cations. The concentration of organic cation in eluate was less than lμg/L. Micelles of ODTMA were used for ethylene dibromide. The residual concentrations of alachlor (less than ppb), and ethylene dibromide were measured by GC-MS. 8TlIe standard deviation was 0.5%; in the case of alachlor (0.005) it was 1%
Table 7
Removal of antibiotics (10 mg/L) by a column filter filled with micelle-clay or activated carbon in the presence of fulvic or humic acid
% Removal Antibiotics Micelle-Clay Activated Carbon
Fulvic acid Humic acid Fulvic acid Humic acid
Tetracycline 99 89 50 81
Sulfamethizole 98 99 50 64
It may be noted that the organic cations employed in the micelle-clay complexes have high affinity for adsorption on montmorillonite (11, 15). Thus any released cations can be completely captured by quartz-clay layer. The results of the present invention demonstrate that the micelle-clay system is efficient for the removal of contaminants from water in the range of milligrams to micrograms per liter. Thus more than 99% removal of organic pollutants was achieved by passage of a solution through a 22 cm layer of quartz mixed with micelle-clay at 100/1 ratio. The implication is that there will be seven to eight orders of magnitude reduction in the concentrations of these pollutants for four passages through similar columns or for one passage through a 1 meter column. Consequently, the level of organic pollutants in water can be easily reduced to any desired level by means of the proposed sand/micelle-clay filter column followed by a sand/clay layer. No difference between elution of compound by methylene chloride or acetone was found.
A carbon analysis was done measuring the amount of the released organic cation from micelle-clay complexes in column-filters for water purification after adding a layer (10cm) of quartz mixed with clay (150:1 w/w) at the bottom of the column. Separate measurements which determined the carbon released from columns filled with quartz or with quartz/clay mixtures are presented in Table 8 (17). The measurements of the Dissolved organic carbon (DOC) showed that the carbon concentration in the filtered water due to the organic cation released from the micelle-clay complexes (0.2 ppm) was less than (or equal within the experimental error) the carbon concentration in the water filtered through the quartz or the quartz- clay mixture. Hence, the carbon analysis showed that in the ppm range all the released cations (ODTMA or BDMHDA) were retained by the column-filter, i.e., by the 10 cm layer of quartz mixed with clay.
In another experiment, the water which eluted or passed through a column filled with quartz mixed with micelle/clay was also passed three times through a 25 cm column filled with quartz-clay (150:1 w/w) and then concentrated 1000-fold. Measurements with GC-MS showed that the concentration of organic cation in the eluate was less than 1 ppb.
Table 8 Carbon content of effluents from 25 cm column
At the bottom of the column was a 3 cm layer of quartz.
Table 9 gives capacities of the micelle-clay filter for removal of several pollutants. The results are expressed as percent (W/W) of the total captured pollutant relative to the weight of the micelle, which is included in the filter (2gr). This presentation reflects the fact that the other components in the filter, i.e., sand and clay are much cheaper than the organic cation. The (W/W) percent values varied from 12.7 to 37.
Table 9
Capacity of the micelle-clay filter for several pollutants expressed as percent (w/w) of pollutant relative to the organic cation.
EXAMPLES
Materials. The clay used was Wyoming Na-montmorillonite SWy-2 obtained from the Source Clays Repository (Clay Minerals Society, Columbia, MO). Quartz sand (grain size 0.8-1.5 mm) was purchased from Negev Industrial Minerals (Israel). Octadecyltrimethylammonium bromide (ODTMA) was purchased from Sigma- Aldrich (Sigma Chemical Co., St. Louis, MO). Benzyldimethylhexadecylammonium chloride (BDMHDA) was purchased from Fluka Chemie (Buchs, Switzerland). Technical sulfentrazone (purity 91.3%) was obtained from FMC (Princeton, NJ); sulfosulfuron (analytical grade) was obtained from E. I. Du Pont de Nemours and Company (Wilmington, DE). Acetochlor, alachlor, imazaquin, and chlorotoluron (all compounds of 98% purity) were supplied by Agan Makhteshim, Israel. Benzoic acid was purchased from Merck (Darmstadt, Germany). Tetracycline hydrochloride, oxytetracycline hydrochloride, chlortetracycline hydrochloride, sulfamethoxazole, sulfisoxazole, and sulfamethizole were purchased from Sigma-Aldrich or Fluka (Switzerland). Structural formulae of surfactants are shown on Figure 1. Seeds of sorghum {{Sorghum bicolor (L.)) from Hazera, (Israel) were used for bioassay tests.
Adsorption. ODTMA and BDMHDA were added to the solutions of pollutants. Pollutant-micelle complexes were kept stirring for 72 h. Then 10 ml of micelle-pollutant complexes were mixed in a polypropylene copolymer centrifuge tube with 5ml of water suspension of montmorillonite. Preliminary experiments showed -no adsorption of
pollutants on the tubes. Concentrations of surfactants in suspensions were 2.5; 5 and 12 niM, i.e., much above their CMC values, which are 0.3 mM and 0.6 niM for ODTMA and BDMHDA, respectively (11, 15). Concentrations of pollutants in suspensions were in the range from 1.33 mg/L to 33.3 mg/L; lower concentrations of 0.16 and 0.005mg/L were also used for acetochlor and alachlor, respectively.
Concentrations of micelle-clay complexes were 2, 5 and 10 g /L. Tubes containing suspensions of pollutants and micelle-clay complexes were kept at 25+1 ° C under continuous agitation for 72 h. Then the tubes were centrifuged for 20 min. at 15000 g and supernatants were passed through teflon filters (ISI, Israel) of 0.2 μm pore diameter and analyzed.
Effect of micelle-clay ratio on the adsorption of imazaquin and acetochlor was studied by using the same technique.
Desorption. Desorption of imazaquin and acetochlor was studied from BDMHD A-clay complex, which was obtained in adsorption experiments at 2.5 mM BDMHDA, 3 g L"1 clay with herbicides. After removing the supernatants 0.045 g of herbicide-micelle-clay complexes were mixed in centrifuge tubes with 15 ml of distilled water; the final complex concentrations were 3g L"1. Tubes were kept at 25+10C under continuous agitation for 1 or 7 days. Then the tubes were centrifuged for 20 min. at 15000 g and concentrations of herbicides in supernatants were measured. Adsorption and desorption experiments were performed in triplicate. Desorption of bromacil was studied from from BDMHDA-clay complex, which was obtained in adsorption experiments at 12 mM BDMHDA, 1Og L"1 clay with herbicide. Adsorption and desorption experiments were performed in triplicate.
Column filter experiments were performed with 100/1 (w/w) mixture of quartz sand and BDMHDA-clay complex in a column of 25 cm length and of 5 cm diameter. Quartz sand was thoroughly washed by distilled water and dried at 105 ° C for 24 h. The micelle-complex was prepared by stirring 2.5 mM of BDMHDA with 2.5 g/L clay for 72h. Then suspensions were centrifuged for 20 min. at 10000 g, supernatants were discarded, and the complex was lyophilized. The column was filled with 700 g sand mixed with 7 g of micelle-clay complex. Non woven polypropylene geo textile filters (Markham Culverts Ltd., Papua New Guinea) were placed on both sides of the column. The column was connected to a peristaltic pump and saturated by distilled water from the bottom (flow 2 or 5 ml/min). hi the case of sulfosulfuron tests indicated that the
same outcome was obtained for flow rates between 2 and 20 ml/min. Estimates indicate that the flow rates can be further increased. Then 1200 mL of 10 mg/L herbicide solution (sulfentrazone, imazaquin, alachlor, acetochlor, chlorotoluron, sulfosulfuron or bromacil) or an antibiotic solution (tetracycline, oxytetracycline, chlortetracycline, sulfamethoxazole, sulfisoxazole, or sulfamethizole) were passed through the column. First 200 ml were analyzed separately and the rest amount was collected and analyzed. Within experimental errors, the results were similar. A solution of 0.005 mg/L of alachlor was passed through this column, collected and then passed sequentially through three columns filled with 150/1 mixture of quartz sand and montmorillonite in order to remove residual organic cations. The experiments were performed in duplicate.
Analysis of pollutants. Solutions were analyzed by HPLC (Merck Hitachi 6200) equipped with a diode array detector. In the experiments with the concentrations of 0.16 mg/L of acetochlor and 0.005mg/L of alachlor measurements were performed by GC-MS.
HPLC column for herbicides was LiChrospherR 100 RP- 18 (5 μM) and the flow rate was 1.0 mL min"1. For anionic pollutants the binary mixtures of organic solvent (acetonitrile or methanol) with water acidified by trifmoroacetic acid to pH 2.95+0.09 were used as mobile phases: acetonitrile/water (50/50) for sulfentrazone; acetonitrile/water (70/30) for sulfosulfuron; methanol/water (60/40) for imazaquin and benzoic acid. For neutral herbicides the following mobile phases were used: acetonitrile/water (70/30) for acetochlor and alachlor; methanol/water (75/25) for chlorotoluron; methanol/water (65/35) for bromacil. The concentrations -of pollutants were measured at the following wavelengths: sulfentrazone at 220 nm, sulfusulfuron at 216 nm, imazaquin at 242nm, benzoic acid at 228 nm, acetochlor and alachlor at 216 nm, chlorotoluron at 248 nm, and bromacil at 280 nm. To analyze the effluent from the column after passing of lOμg/L of sulfamethizole, the sample was extracted by solid- phase extraction using 3M Empore TM SDS-RPS (47 mm) extraction discs (Varian, CA, USA) and vacuum manifold. Disc was consecutively conditioned with 5 ml and 15 ml of acetonitrile followed by drying under the vacuum after each step of conditioning. Then next 15 ml of acetonitrile was added followed by 15 ml of double-distilled water. One liter of sample was passed through the conditioned disc. Sulfamethizole was consecutively eluted three times by 5 ml of acetonitrile followed by 5 ml of methanol. The eluent was evaporated to 1ml at 60°C under gentle stream of nitrogen. HPLC
colunin for antibiotics was 3.9x150 mm Waters Nova Pak C8 (4 μm) and the flow rate was 1.0 mL min"1. For tetracyclines a ternary mixture of 0.05M K2PO4 solution acidified by H3PO4 acid to pH 2.25+0.09 with acetonitrile and methanol (75/15/ 10) used as mobile phases. For sulfa drugs a ternary mixture of 0.05M NH4CH3COO solution acidified by H3PO4 acid to pH 2.4+0.1 with acetonitrile and methanol (70/27/ 3) was used. The concentrations of tetracyclines were measured at 270 nm, the concentrations of sulfa drags were measured at 280 nm.
For GC-MS analysis water samples of acetochlor and alachlor were extracted by SPE technique using vacuum manifold and a standard Millipore 47 mm filtration apparatus (Bedford, MA). Acetochlor was extracted by the empore extraction disks, 47 mm with C18 phase from Varian (Harbor City, CA) and eluted by ethyl acetate, methylene chloride and their 50/50 mixture. The extracts were passed through the tube with anhydrous sodium sulphate to get rid of residual molecules of water. Then the extracts were evaporated to a volume of 1ml with gentle stream of nitrogen at 40°C. GC-MS measurements were performed with (TermoQuest GC Trace2000 Polaris Instrument) fitted with DB-5.MS capillary column, 30m * 0.25mm i.d. x 0.25μm film thickness from J&W Scientific (CA, USA) The carrier gas was helium (linear velocity was 33cm/s). Injector temperature was 25O0C. The oven temperature was held at 450C for 2min, then raised at 40°C/min to 16O0C, followed by 5°C/min to 21O0C and finally raised at 40°C/min up to 28O0C. The transfer line temperature was 2950C. Phenantren D10 was used as internal standard.
The eluates obtained from column filter experiment for alachlor analysis were filtered through Whatman GF/C filter followed by ME 25 filters with 0.45-μm pore diameter (Schleicher & Schull, Dassel, Germany). Then alachlor was extracted by the ENVI ™ extraction disks, 47mm with C18 phase from Supelco (Bellefonte, PA) and eluted be methylene chloride. Then the extracts were evaporated to a volume of ImI with gentle stream of nitrogen. GC-MS measurements were performed with Saturn 2000 GC-MS (Varian, Walnut Creek CA) equipped with SPB ™"5 capillary column, 30m x 0.25 mm i.d. x 0.25μm film thickness from Supelco (Bellefonte, PA) The carrier gas was helium (linear velocity was 50 cm/s). Injector temperature was 28O0C. The oven temperature was held at 5O0C for 2min, and then raised at 5°C/min to 26O0C. The transfer line temperature was 3000C. Biphenyl was used as internal standard.
Bioassay. A bioassay analysis enables easy detection of certain herbicides at level of 1 μg/L. A solution of 200 ppb was passed through the column filter filled with the 100/1 mixture of quartz sand with BDMHD A-complex. Bioassay tests were performed in 9-cm Petri dishes filled with quartz sand (135g per dish). Solutions containing different concentration of sulfosulfuron were added to the dishes (15 ml per dish) to check dose-response of sorghum for the herbicide and to obtain a calibration curve as reported in (18). The eluate from the column was added to Petri dishes. Four replicas were performed for each concentration and for eluate. Sorghum seeds were planted in the sand 1 cm from the bottom of each dish. After sowing, the dishes were sealed and incubated in a dark room at 28° C tilted face up at 80° angles. The root lengths were measured after 3 days of incubation. A calibration curve in bioassay test, was simulated reasonably well (R2= 0.91) by the equation: y=7.789e ° 687x, in which y is root length in cm and x is the concentration of sulfosulfuron in μg/L. The average length of the roots of the plants, which were treated by the eluate from the column filter, corresponded to a concentration of 1.08 μg/L.
REFERENCES
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Claims
1. A method for purifying an aqueous solution from neutral or anionic pollutants present therein comprising contacting the polluted aqueous solution with a mixture of (i) a granular material and (ii) a complex comprising micelles of an organic cation adsorbed on clay;
2. The method of claim 1 wherein the ratio (w/w) between the granular material and said complex being in the range of 5:1 to 200:1, preferably 50:1 to 120:1 and most preferably 75:1 to 100: 1.
3. A method according to claim 1, wherein the ratio of the organic cation and the clay is 0.3:1 to 0.7:1 (w/w).
4. A method according to claim 3 wherein the ratio of the organic cation and the clay is 0.4:1 to 0.6:1
5. A method according to claim 4 wherein the ratio of the organic cation and the clay is 0.45:1 to 0.5:1.
6. A method according to any one of claims 1-5 wherein the granular material has an average particles size from 0.2mm to 2mm.
7. A method according to any one of claims 1-6, wherein said granular material is sand.
8. A method according to any one of claims 1-7, wherein the clay is an aggregate of hydrous silicate particles having a diameter of less than about 4μm.
9. A method according to Claim 8, wherein the clay is selected from kaolinite- serpentine, illite, and smectite.
10. A method according to any one of claims 1-9, wherein said contacting is by passing the polluted water through a container comprising said mixture.
11. A method according to Claim 10, wherein said container is a column.
12. A method according to any one of claims 1-11 wherein said organic cation has a low critical micelle concentration of less than 1 mM.
13. A method according to claim 12, wherein the organic cation is an ammonium cation of the type X+Y" wherein X+ is an R"-N(R')3, R being each independently a Ci- 4alkyl group, an optionally substituted phenyl or an alkylphenyl group; R" is C12-C20- alkyl preferably C14-C20-alkyl, most preferably C16-C20-alkyl and Y" is a counter ion.
14. A method according to claim 13 wherein Y is selected from Cl", Br" or OH",.
15. A method according to claim 13 wherein at least one of the R1 groups is methyl, ethyl, propyl, pheny, benzyl and R" is C14H29, C15H31, C16H33, C16H31, C17H35, Ci7H33, Ci8H37, C18H35, C19H39 C19H37, C20H41, C20H39.
16. A method according to any one of claims 1-15, wherein said neutral or anionic pollutants are organic pollutants.
17. A method according to claims 16 wherein the neutral pollutants are selected from the group comprising of neutral herbicides and halogenated Ci-8alkyls.
18. A method according to claim 17, wherein the neutral herbicides are selected from chloroacetamides, uracils or ureas and the halogenated C1-8alkyls are C1. δhalogenoalkenyls, Ci-8halogenoalkynyls which optionally may be perhalogenated.
19. A method according to claim 18, wherein said neutral pollutants are selected from the group consisting of alachlor, acetachlor, bromacil, chlorotoluron, isoproturon, isouron, propachlor, dimethachlor, lenacyl, terbacil and the halogentated Ci-8 moieties are methyl, ethyl, ethenyl, ethynyl, propyl, propenyl, propynyl, butyl, butylenyl, butynyl, pentyl, pentenyl, pentynyl hexyl, hexenyl, hexynyl comprising at least one halogen.
20. A method according to claim 16, wherein said anionic pollutants are selected from the group consisting of imidazolinones, triazolinones, sulfonylurea, aromatic carboxylic acids, humic acid or fulvic acid, antibiotics or their mixtures.
21. A method according to claim 20, wherein said anionic pollutants are selected from the group consisting of imazaquin, imazethapyr, imazapyr, imazamethabenz- methyl, imazamox, imazapic, chlorsulfuron, imazosulfuron, pyrazosulfuron-ethyl, primisulfuron, -methyl, nicosulfuron, bensulfuron-methyl, amicarbazone, azafenidin, sulfentrazone, sulfo sulfur on, tetracyclines and antibacterial agents .
22. A composition comprising a mixture of (i) a granular material; and (ii) a complex comprising micelles of an organic cation adsorbed on clay;
23. A composition according to claim 22 wherein the ratio (w/w) between the granular material and said complex being in the range of 5:1 to 200:1, preferably 50:1 to 120:1 and most preferably 75:1 to 100: 1.
24. A container comprising a mixture of (i) a granular material; and (ii) a complex comprising micelles of an organic cation adsorbed on clay;
25. A container according to claim 24 wherein the ratio (w/w) between the granular material and said complex being in the range of 5:1 to 200:1, preferably 50:1 to 120:1 and most preferably 75:1 to 100: 1.
26. A system for purifying an aqueous solution from neutral and/or anionic pollutants present therein, the system comprising at least one container adapted to receive the polluted aqueous solution and containing a mixture of (i) a granular material and (ii) a complex comprising micelles of an organic cation adsorbed on clay.
27. The system according to claim 26 wherein the ratio (w/w) between the granular material and said complex being in the range of 5:1 to 200:1, preferably 50:1 to 120:1 and most preferably 75:1 to 100: 1 .
28. A system according to claim 26 or 27, wherein the ratio of the organic cation and the clay is 0.3:1 to 0.7:1 (w/w), preferably 0.4:1 to 0.6:1, most preferably 0.45:1 to 0.5:1.
29. A system according to any one of claims 26-28, wherein the granular material has an average particles size from 0.2mm to 2mm.
30. A system according to any one of claims 26-29, wherein said granular material is sand.
31. A system according to any one of claims 26-30, wherein the clay is an aggregate of hydrous silicate particles having a diameter of less than about 4μm.
32. A system according to any one of claims 26-31, wherein the clay is selected from kaolinite-serpentine, illite, and smectite, preferably a smectite, most preferably montmorillonite.
33. A system according to any one of claims 26-32 wherein the container is a column.
34. A system according to any one of claims 26-32 wherein the organic cation adsorbed on the clay as a micelle has a low critical micelle concentration of less than 1 mM.
35. A system of any one of claims 26-34, wherein the organic cation is an ammonium cation of the type X+Y' wherein X+ is an R"-N(R')3, R' being each independently a C1-4alkyl group, an optionally substituted phenyl or an alkylphenyl group; R" is C12-C20-aUcyl preferably C14-C2o-alkyl, most preferably C16-C2o-alkyl and Y" is a counter ion.
36. A system according to claim 26 wherein the counter ion is selected from: Cl", Bf5 or OH".
37. A system according to claim 35, wherein R' is methyl, ethyl, propyl, phenyl, benzyl and R" is C14H29, Ci5H31, C16H33, Ci6H31, CnH35, C17H33, C18H37, C18H35, C19H39 Ci9H37, C20H4I, C20H39.
38. A system according to any one of claims 26-37, wherein said container further comprises an additional layer at its bottom having a layer being about 7-10% of the total volume of the container , said layer comprising sand or a mixture of sand and clay.
39. A system according to any one of claims 26-38 comprising two or more containers.
40. A system according to claim 39, wherein at least one container comprises a plurality of alternating first and second layers, said first layer comprises sand or sand and clay and said second layer comprises a mixture of (i) a granular material and (ii) a complex comprising micelles of an organic cation adsorbed on clay.
41. A method for purifying water, comprising adding into the water either (i) micelles of an organic cation and particulate clay, to yield a complex, or (ii) a complex of micelles of an organic cation and particulate clay.
42. A method according to claim 41, wherein the particulate clay is added to the water after the addition of said micelles.
43. A method according to claim 42, comprising an incubation step prior to addition of the particulate clay.
44. A method according to any one of claims 41-43, comprising allowing sedimentation of said complex and removing the sediment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64402205P | 2005-01-18 | 2005-01-18 | |
| PCT/IL2006/000072 WO2006077583A1 (en) | 2005-01-18 | 2006-01-18 | Removal of organic pollutants from contaminated water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1851173A1 true EP1851173A1 (en) | 2007-11-07 |
| EP1851173B1 EP1851173B1 (en) | 2013-11-20 |
Family
ID=35840590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06728167.5A Expired - Lifetime EP1851173B1 (en) | 2005-01-18 | 2006-01-18 | Removal of organic pollutants from contaminated water |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20090114599A1 (en) |
| EP (1) | EP1851173B1 (en) |
| AU (1) | AU2006207215A1 (en) |
| WO (1) | WO2006077583A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10384959B2 (en) | 2014-07-03 | 2019-08-20 | Shlomo Nir | Method of making and using granulated micelle-clay complexes for removal of pollutants from water |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008139474A1 (en) | 2007-05-14 | 2008-11-20 | En Gibton Ltd. | Method and system for removal of inorganic anionic pollutants from contaminated water |
| JP2014157091A (en) * | 2013-02-15 | 2014-08-28 | Central Research Institute Of Electric Power Industry | Device and method for measuring age of groundwater |
| CN104108764B (en) * | 2014-07-09 | 2016-02-03 | 山东大学 | A kind of restorative procedure to microbiotic drug contamination waste water |
| CZ305778B6 (en) * | 2014-12-31 | 2016-03-09 | Vysoká Škola Báňská - Technická Univerzita Ostrava | Filter for removing both inorganic and organic substances from contaminated water |
| US10155675B2 (en) | 2015-12-21 | 2018-12-18 | International Business Machines Corporation | Method for removing glyphosate from a solution |
| CN112044393B (en) * | 2019-06-06 | 2021-05-04 | 中南大学 | A kind of two-dimensional clay-based composite phosphorus removal agent and its preparation method and application |
| CN111362348A (en) * | 2020-04-14 | 2020-07-03 | 南京融众环境工程研究院有限公司 | Method for removing prosulfuron in water body by using montmorillonite adsorbent |
| CN111704218A (en) * | 2020-06-19 | 2020-09-25 | 德蓝水技术股份有限公司 | Special flocculating agent for industrial wastewater and preparation method thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2367384A (en) * | 1942-09-22 | 1945-01-16 | Shell Dev | Method of removing oil from water |
| US3741390A (en) * | 1971-12-13 | 1973-06-26 | Harsco Corp | Tertiary filter |
| US4386010A (en) * | 1980-09-02 | 1983-05-31 | Engelhard Corporation | Treated attapulgite clay composition |
| US4549966A (en) * | 1982-09-20 | 1985-10-29 | Radecca, Inc. | Method of removing organic contaminants from aqueous compositions |
| US4916095A (en) * | 1988-07-14 | 1990-04-10 | The University Of Michigan | Modified clay sorbents |
| US5401417A (en) * | 1993-07-30 | 1995-03-28 | University Of Delaware | Selective adsorption of organic material from water by modified clays |
| US5512526A (en) * | 1995-01-06 | 1996-04-30 | Akzo Nobel N.V. | Heavy metal removal system containing clay, quaternary ammonium compound, and mercaptan |
| US5667694A (en) * | 1995-08-28 | 1997-09-16 | Rheox, Inc. | Process for the removal of heavy metals from aqueous systems using organoclays |
| US6054052A (en) * | 1995-12-14 | 2000-04-25 | Mobil Oil Corporation | Selective sorption of organics by metal-containing M41S |
| US6080319A (en) * | 1998-06-18 | 2000-06-27 | Biomin Inc. | Chemical methods for removing contaminants from water |
| US6524485B1 (en) * | 1999-09-17 | 2003-02-25 | Advanced Research And Technology Institute, Inc. | Polymer-micelle complexes and methods of use thereof |
| US6503740B1 (en) * | 2000-02-22 | 2003-01-07 | Biomin, Inc. | Organically modified mineral materials containing engrafted bacteria for chemical contaminant decomposition |
| ES2262806T3 (en) * | 2001-01-03 | 2006-12-01 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | FORMULATIONS OF CONTROLLED RELEASE OF ANIONIC HERBICIDES. |
| US6627084B2 (en) * | 2001-04-24 | 2003-09-30 | Polymer Ventures, Inc. | Organoclay compositions for purifying contaminated liquids and methods for making and using them |
-
2006
- 2006-01-18 AU AU2006207215A patent/AU2006207215A1/en not_active Abandoned
- 2006-01-18 WO PCT/IL2006/000072 patent/WO2006077583A1/en not_active Ceased
- 2006-01-18 EP EP06728167.5A patent/EP1851173B1/en not_active Expired - Lifetime
- 2006-01-18 US US11/814,171 patent/US20090114599A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2006077583A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10384959B2 (en) | 2014-07-03 | 2019-08-20 | Shlomo Nir | Method of making and using granulated micelle-clay complexes for removal of pollutants from water |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2006207215A1 (en) | 2006-07-27 |
| EP1851173B1 (en) | 2013-11-20 |
| WO2006077583A1 (en) | 2006-07-27 |
| US20090114599A1 (en) | 2009-05-07 |
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